Study of the optically diffused reflectance and thermal-microstructure for the phase transformation of AgNO3

Optical, microstructural, and thermal properties of the investigated silver nitrate samples were characterized by various techniques, such as X-ray analysis, scanning electron microscopy, UV–Vis–NIR absorption and differential scanning calorimetry (DSC). The presence of structural phase transition [orthorhombic structure (phase II) to rhombohedral structure (phase I)] was checked by DSC and X-ray analysis measurements. The thermal energy required for such transformation is found to be 11.6 J/g. The optical band gaps of AgNO₃ are 1.4 and 2.02 eV for phase II and phase I, respectively, at the low-energy region. But at high-energy region, the optical band gaps are 3.41 and 3.43 eV for phase II and phase I, respectively. Characteristic peaks for AgNO₃ corresponding to (2 1 1), (0 0 4) and (3 5 1) for phase II and (0 0 4), (3 1 1) and (0 2 4) for phase I have been observed. The average crystalline size for AgNO₃ samples and the values of dislocation density δ and the strain ε for the planes of two phases II and I are calculated and also the texture coefficient is determined. Such information can considerably aid in understanding the process of phase transformations in AgNO₃.     

Changes in the electronic structure upon the B2–B19′ martensitic transformation in titanium-nickel

The self-consistent band structure of a TiNi intermetallic compound in two phases is calculated by the full-potential linearized augmented-plane-wave (FLAPW) method. The features of changes in the density of states upon B2–B19′ martensitic transformation are discussed. The influence of atomic positions on the electronic structure of the martensitic monoclinic phase is examined. The frequency dependence of the optical conductivity and the emission, absorption, and the characteristic electron-energy-loss spectra are calculated with due regard for the transition probability matrix element. The results of calculations are in reasonable agreement with the available experimental data.     

GaN结构相变、电子结构和光学性质

运用第一性原理平面波赝势和广义梯度近似方法,对纤锌矿结构和氯化钠结构GaN的状态方程及其在高压下的相变进行计算研究,分析相变点附近的电子态密度、能带结构和光学性质的变化机制.通过状态方程和焓相等原理得到GaN从纤锌矿到氯化钠结构的相变压强分别为43.9 Gpa和46.0 Gpa;在相变的过程中,GaN由典型的直接带隙半导体转变为间接带隙半导体材料;氯化钠结构GaN相比于纤锌矿结构,介电函数主峰值增强,本征吸收边明显往高能方向移动,氯化钠结构GaN在低能区域的光学性质差于纤锌矿结构.     

Temperature and pressure derivatives of elastic constants in single crystal Au-47.5 at.% Cd near martensitic phase transformation

The behavior of the elastic properties and their pressure derivatives near the martensitic transformation β→β′ was determined from sound velocity measurements at a frequency of 10 MHz, on a single crystal of Au-47.5 at.% Cd.The transformation of the β phase to the martensitic β' phase was obtained from the anisotropic elastic constants c₁₁, c₄₄ and c′, and their pressure derivatives. The behaviour of c₁₁ and c₄₄ is normal as a function of temperature, while the variation of c′ is positive with temperature. Before the β→β′ phase change the value of c′ is very small and exhibits high elastic anisotropy. The small value of c′ and the anisotropy were explained according to the crystallographic mechanism of the martensitic transformation and the Zener theory of instability of the b.c.c. structure. The pressure derivatives of c′ are negative and the variation of $\text{d}\text{c}{}_{44}\text{d}\text{P}$ with temperature is anomalous. This behavior can be explained by the influence of pressure on the transformation temperature, and by the instability of the β phase. It was found that the elastic constants c′ determine the mechanism of the transformation. From the pressure derivatives of c₁₁, c₄₄ and c′ the Grüneisen parameters for different modes of vibration were calculated. For the c′ mode the values are negative, for the c₄₄ mode the variation of the parameter with temperature is negative. This anomalous behavior can be explained as due to the anisotropic softening of the atom bonding on the (110) planes of the cubic structure, as a consequence of the phase transformation mechanism.     

GaP相变及热力学性质的理论研究

利用基于密度泛函理论的第一性原理方法研究了闪锌矿和氯化钠结构的GaP的相变及热力学性质.对两种结构的能量体积曲线做公切线,得到了从闪锌矿到氯化钠结构的相变压力约为26.2GPa,与实验结果一致.通过准谐德拜模型得到了不同温度下体积和热膨胀系数与压强的关系,以及不同压强下热容与温度的关系.     

Lattice dynamics and statistical mechanics of the Fm3m → I4/m structural phase transition in Rb2KInF6

The static and dynamic properties of cubic Rb₂KInF₆ crystals with elpasolite structure are calculated using a nonempirical method. Calculations are performed within a microscopic ionic-crystal model taking into account the deformation and polarization of ions. The deformation parameters of ions are determined by minimizing the total energy of the crystal. The calculated equilibrium lattice parameters agree satisfactorily with the experimental data. It is found that in the cubic phase there are vibrational modes that are unstable everywhere in the Brillouin zone. The eigenvectors of the unstablest mode at the center of the Brillouin zone of the cubic phase are associated with the displacements of F ions and correspond to rotations of InF₆ octahedra. Condensation of this mode leads to a tetragonal distortion of the structure. In order to describe the Fm3m → I4/m phase transition, an effective Hamiltonian is constructed under the assumption that the soft mode whose eigenvector corresponds to octahedron rotation is local and coupled with homogeneous elastic strains. The parameters of the effective Hamiltonian are determined using the calculated crystal energy for the distorted structures due to soft-mode condensation. The thermodynamic properties of the system with this model Hamiltonian are investigated using the Monte Carlo method. The phase transition temperature is calculated to be 550 K, which is twice its experimental value (283 K). The tetragonal phase remains stable down to T=0 K; the effective Hamiltonian used in this paper thus fails to describe the second phase transition (to the monoclinic phase). Thus, the transition to the tetragonal phase occurs for the most part through octahedron rotations; however, additional degrees of freedom, first of all, the displacements of Rb ions, should be included into the effective Hamiltonian in order to describe the transition to the monoclinic phase.     

Carbon systems of polymerized nanotubes: Crystal and electronic structures

Molecular dynamic calculations are carried out for the (P, T) phase diagram of a covalent compound of cross-linked carbon single-wall nanotubes (SWNT) and for the structures and electronic spectra of the novel crystals of polymerized carbon nanotubes. It is shown that the transformation of covalently bonded nanotubes in a close-packed conducting structure cardinally modifies their electronic properties. The P-SWNT crystal becomes semiconducting and, upon complete transformation of sp ²-hybridized carbon atoms into sp ³-hybridized ones, it becomes an insulator.     

Austenitic structure formation in an Fe-32% Ni alloy during slow heating in the critical temperature range

Electron diffraction is used to show (for the first time) that the reverse α → γ transformation in an Fe-32% Ni during slow heating develops via the formation of an intermediate paramagnetic 9R phase. Coarse extended lamellae form according to a shear mechanism in the central part of the temperature range of the reverse transformation, which is called the critical range (here, the physical properties of the alloy change anomalously). The extended lamellae consist of 9R-phase lamellae with γ-phase interlayers. A high density of periodic stacking faults in the structure of the 9R phase and a high density of chaotic stacking faults in the complex 9R + γ phase determine the nature of phase transformation-induced hardening.     

High-pressure Raman and infrared study of ZrV 2O7

The room-temperature Raman and infrared spectra of zirconium vanadate (ZrV ₂O₇) were observed up to pressures of 12 GPa and 5.7 GPa, respectively. The frequencies of the optically active modes at ambient pressure were calculated using direct methods and compared with experimental values. Average mode Grüneisen parameters were calculated for the Raman and infrared active modes. Changes in the spectra under pressure indicate a phase transition at ∼1.6 GPa, which is consistent with the previously observed α (cubic) to β (pseudo-tetragonal) phase transition, and changes in the spectra at ∼4 GPa are consistent with an irreversible transformation to an amorphous structure.     

Amorphous Heusler alloys: The effect of annealing on structure and magnetic and transport properties

Alloys with the Heusler compositions Cu₂MnIn, Cu₂MnAl and Cu₂MnSn have been prepared as amorphous films for the first time. The structural disorder results in as-deposited films which are not ferromagnetic and, in fact, exhibit spin-glass properties due to the distribution of MnMn distances and co-existence of positive and negative exchange interactions. Annealing of the In and Al alloys can restore single phase ordered Heusler structures which are ferromagnets with Curie temperatures typical of bulk alloys. The calculated Mn moments remain lower than the bulk values of 4 μ_B probably due to disorder at grain boundaries. Films annealed under non-optimum conditions crystallized into several non-magnetic structures as well as the magnetic L2₁ Heusler phase. Lattice constants of all phases were determined. The temperature dependence of resistivity through the amorphous-crystalline transformation was found to confirm the results of thermal annealing on structure and magnetization.     

First-principles study of electronic structure and optical properties of Sr(Ti,Zr)O3

Electronic and optical properties of Sr(Ti,Zr)O₃ crystals in the cubic (Pm-3m) and tetragonal (I4/mcm) phase were calculated by the first-principles calculations using the density functional theory and the local density approximation. The band structure of cubic and tetragonal phases show an indirect band gap at (R-Γ) point and at (M-Γ) point in the Brillouin zone, respectively. The linear photon-energy dependent dielectric functions and some optical properties such as the absorption coefficient, energy-loss function and reflectivity are calculated for both phases. The optical properties of tetragonal phase of Sr(Ti,Zr)O₃ were investigated by theoretical methods for the first time. We have also made some comparisons with the available related experimental and theoretical data.     

固氢金属化转变压力的理论计算

 利用简单金属的赝势理论方法计算了固氢的金属转变压力,并探讨了金属氢可能的晶体结构及力、热物性。计算结果表明,在绝对零度条件下,分子态固氢（HCP结构）向原子相金属氢（FCC结构）的转变压力p_t=465.95 GPa。     

Formation of a Cmcm phase in SnS at high pressure; an ab initio constant pressure study

The stability of SnS at high pressure is studied using a constant pressure ab initio technique. For the first time, a pressure-induced phase transformation from the Pnma structure to a Cmcm structure with the application of pressure is predicted through the simulations in this material. The Cmcm phase is still a layered structure, consisting of rocksalt-like bilayers, similar to that formed at high temperatures. The Cmcm structure is fivefold coordinated. This phase transformation gradually proceeds and is due to the significant decrease of the second neighbor distances. This phase change is also studied by total energy calculations.     

Baroelastic shape memory effects in titanium nickelide alloys subjected to plastic deformation under high pressure

The effects of a high pressure and torsional plastic deformation in Bridgman anvils on the structure and phase transformations in titanium nickelide-based shape memory alloys are studied by electron microscopy, neutron diffraction, and X-ray diffraction. The physical properties of the alloys are measured. It is found that the baroelastic effects related to the highly reversible B2 ? B19?? martensitic transformation can occur in metastable austenitic titanium nickelide alloys in both the standard polycrystalline and nanocrystalline states under high pressure.     

加压下ZnO结构相变和电子结构的第一性原理计算

基于密度泛函(DFT)理论的第一性原理,计算半导体ZnO纤锌矿结构和岩盐矿结构状态方程及其在高压下的相变,分析加压下体相ZnO的晶格常数、电子态密度和带隙随压力的变化关系,并将计算结果与文献中的理论和实验数据进行比较.验证在计算金属氧化物时,应用局域密度(LDA)近似计算出的相变压力普遍偏高,采用广义梯度(GGA)近似得到的结果与实验符合较好.     

Prediction of a bcc-hcp phase transition for Sn: A first-principles study

The high-pressure structural transformation of elemental Sn is studied using an ab initio density functional theory implementation of the metadynamics method that predicts with sufficient compression, Sn will transform from the bcc structure into an hcp structure. The low-free-energy pathway associated with this phase transition is characterized as the Burgers transition mechanism. The superconducting properties of Sn under pressure are also investigated. Both bcc and hcp structures of Sn exhibit very weak electron-phonon coupling and therefore would not sustain superconductivity at high pressure.     

Ab initio study of phase transition and thermodynamic properties of PtN

The transition phase of PtN from zincblende (ZB) structure to rocksalt (RS) structure is investigated by ab initio plane-wave pseudopotential density functional theory method, and the thermodynamic properties of the ZB and RS structures under high pressure and temperature are obtained through the quasi-harmonic Debye model. The transition phase from the ZB structure to the RS structure occurs at the pressure of 18.2 GPa, which agrees well with other calculated values. Moreover, the dependences of the relative volume V/V₀ on the pressure P, the Debye temperature Θ and heat capacity C_V on the pressure P, together with the heat capacity C_V on the temperature T are also successfully obtained.     

Transition phase and thermodynamic properties of GaN via first-principles calculations

The transition phase of GaN from zincblende (ZB) structure to rocksalt structure (RS) is investigated by ab initio plane-wave pseudopotential density functional theory method, and the thermodynamic properties of the ZB and RS structures are obtained through the quasi-harmonic Debye model. We find that the transition phase from the ZB structure to the RS structure occurs at the pressure of 42.2 GPa, which is in good agreement with other calculated values. Moreover, the dependences of the relative volume V/V₀ on the pressure P, the Debye temperature Θ and heat capacity C_V on the pressure P, as well as the heat capacity C_V on the temperature T are also successfully obtained.     

Transition from antiferromagnetic to ferromagnetic state of systems LaMnO3+λ and La1−x Srx(Mn1−x/2Nb x/2)O3

The crystal structure and magnetic and elastic properties of the system LaMnO_3+λ are investigated for various concentrations of oxygen. Upon an increase in the oxygen concentration, the orbital-ordered phase is transformed into an orbital-disordered phase via a two-phase crystal-structure state in the interval 0.04<λ<0.06. The transition is accompanied by a jumplike increase in the Curie temperature and spontaneous magnetization. An analysis of the magnetic properties in weak fields and of the temperature dependence of the Young modulus reveals the properties typical of the orbital-ordered antiferromagnetic phase up to λ=0.08. It is proposed that the two-phase state is associated with the martensite type of the orbital order-disorder phase transformation. The system La_1?x Sr_x(Mn_{1 ?x/2}Nb _x/2)O₃ in which all manganese ions are in the trivalent state exhibits a sequence of antiferromagnetic-ferromagnetic (x>0.2) and ferromagnetic-spin glass (x>0.4) transitions. In both systems, the orbital-disordered phases are ferromagnetic, indicating the crucial role of orbital ordering in the formation of magnetic properties.